Method for preparing substituted hydroxy benzyl alcohol



Patented Mar. It}, 1953 and Y is selected fromthe group consisting of high boiling petroleum ether, filtered hot, and

'UNI'TEEZYVSTATES PATENT- ori ice METHOD FOR PREEARING SUBSTITUTED HYDROXY BENZYL ALCOHOL N Drawing. Application September 12, 1950, Serial No. 184,522

8 Claims. (Cl. 266-622) a 2 The invention relates to a, process for the washed with an additional 100 parts of petroleum preparation of certain substituted. hydroxy ether. This extraction was performed to remove benzyl alcohols. any unreacted trichlorophenol which may. have More particularly the invention relates to a been present. new process for thepreparation of compounds 5 The insoluble residue weighed 35 parts and having the followinggeneral formula: had a. melting-point of 90-6 C. This product OR was recrystallized from 75 parts benzene, Washed with low boiling petroleum ether, and dried. A *CHZOH crystalline product weighing 22 parts and having a melting point of 121.5-l23 C. was obtained. A small sample was dissolved twice in boiling benzene, treated with Norite and filtered hot. Two subsequent recrystallizations from benzene yielded a white product which was dried wherem X1 and X2 e Selected, from the group at 95-100 C. for six hours. This solid had a consisting of chlorine, bromine, and nitro groups melting point f 12340 G The compound was-2-hydroxy-3,5,6-trichloro chlorine and bromine groups; benzylalcohol' Certain reactmns and mmaldehyde Analysis: Calculated for 0711502013 (227.5): c are known. Howeven'ithas not been known to 3696; H, 221, C1 ,ycfifmv Found: C, 3631; produce benzyl alcohols by reaction with the less 227; C1, reactive type substituted phenols of thepresent Dilution of the mother application.

According to the present invention substituted hydroxyl benzyl alcohols of the above general formula are prepared by reacting the corresponding substituted phenol at an elevated temof 924090 one recrystallization from hem perature with formaldehyde in the presence of zene yielded an orange solid which melted at alkali, e. g. alkali metal hydroxides. Preferably 1094140 0 an excess of formaldehyde is used and the phenol 3O liquor with water produced a dark red oil which solidified on standing. The solid was filtered off and washed with water. The dry material weighed 20 parts (22% of the theoretical yield) and had a melting point Example 2 dropped into it. One mol or more alkali 1s preferably used per mol of phenol and the tempera- (NOtebWk 2632-100) ture is in the range of 40 to 50 C. for a time in In a flask equipped t stirrer and t e r e of 0 0 15 o d n the eter was placed 653 parts of aqueous formperature is brought to and maintained in the 35 aldehyde which was t heated to C. A range of fll at least One 1101111 lution of 500 parts of steam distilled 2,4,5-tri- The following examples are illustrative of emchlgrophenol m p 59 3 C and 02 parts of bodiments of the invention but substitutions and sodium hydroxide pe11ets in 1270 parts ater alterations may be made within the scope of the was added gradually t th ti d formaldehyde claims 40 at 40-50 c. This addition required fifty-five Example 1 minutes. The reaction mixture was stirred at -50 C. for fifteen hours, heated to 88 C. in

In a flask equipped with stirrer and thermom" one hour and ten minutes, and held at 87-9l C. 91791 was Placed 102-6 parts 35% aqueous form for one hour. The reaction mixture was placed aldehyde which was then heated to 45 in an ice bath and cooled to 38 in fifteen min- A Solution of Parts ziii5'tl'ichlorophenol utes. The orange solid obtained by neutralizaand parts Sodium hydroxide Pellets in 109 tion was filtered, washed with water, and airparts water was added gradually to the stirred dried, There was obtained 393 parts 73% formaldehyde at 45-50 C. This addition reyield) f lidmeltingat106 110C quired ten minutes. The reaction mixture was stirred at 45-50" C. for fourteen hours, then Example 3 heated to C. in one hour and held at 60-65" C. Using the same amounts as Example 2 the profor two hours. The mixture was neutralized by cedure of Example 1 was followed except that the passing in carbon dioxide gas, and an orange reaction mixture was stirred at 45-50" C. for 10 solid precipitated out. This solid was collected 55 hours, 5050 C. for 1 /2 hours, and Gil- C. for by filtration, washed well with water and dried 2 hours. A semi-solid mass was formed upon in a vacuum desiccator. The crude dry product neutralization; this material was extracted with weighed 35.7 parts (39.2% of the theoretical ether and treated as in Example 2. There was yield) and had a melting-point of 96 C. This obtained 38A parts of crude product. After treatcrude material was stirred with parts of hot 60 ment with petroleum ether, 22 parts (48.4% of the theoretical amount) of product was obtained with a melting point of 109-l12 C. Three recrystallizations raised the melting point to 123-4C.

Analysis Calcd. for CIHsOzCls (227.5): Cl, 46.76%. Found: Cl, 45.90; 45.67

Example 4 The procedure of Example 1 was repeated using 391 parts of purified 2,4,5-trichlorophenol, M. P. 64-66 0., 510 parts of 35% aqueous formaldehyde, 79 parts sodium hydroxide and 495 parts of water. The reaction mixture was stirred 13 hrs. at 45-50 and 3% hr. at 65-70 C. There was obtained 215 parts (47.7% yield) of solid melting at 105-113 C. No extraction with petroleum ether was necessary. After one recrystallization from benzene, 125 parts of product melting at 116-118" C. was obtained.

It had the following analysis:

Calcd. for CIH5O2C13 (227.5) C1, 46.76%. Found: Cl, 46.57

In a similar manner, 2,4,5-tribromophenol, 2,4- dinitro-B-bromophenol and 2,5-dinitro-5-chlorophenol may be reacted as in Example 1 above to give the corresponding substituted benzyl alcohol.

These compounds are useful as intermediates for the preparation of germicides and may themselves be germicides. The 2-hydroxy-3,5,6-trichloro benzyl alcohol is of particular importance for this purpose when reacted with other substituted phenols.

What we claim is:

1. A process for preparing a compound of the general formula,

wherein X1 and X: are selected from the group consisting of chlorine, bromine, and nitro groups and Y is selected from the group consisting of chlorine and bromine groups, which comprises reacting the corresponding substituted phenol with an excess of formaldehyde in the presence of aqueous alkali metal hydroxide catalyst at a temperature in the range of 40 to C. for a time in the range of 10 to 15 hours, and then at a temperature in the range of to C. for at least one hour.

2. A process of claim 1 wherein the alkali is sodium hydroxide.

3. A process of claim 2 wherein the phenol reactant is slowly added to the formaldehyde.

4. A process of claim 3 wherein about one mol of the sodium hydroxide is used per mol of the phenol reactant.

5. A process of claim 4 applied to the preparation of 2-hydroxy-3,5,6-trichloro benzyl alcohol.

6. A process of claim 4 applied to the reparation of 2-hydroxy-3,5,6-tribromo benzyl alcohol.

7. A process of claim 4 applied to the preparation of 2-hydroxy-3,5-dinitro-6-chloro benzyl alcohol.

8. A process of claim 4 applied to the preparation of 2-hydroxy-3,5-dinitro-6-bromo benzyl alcohol.

MAX E. CHIDDIX. MARJORIE R. WILLIAMS.

REFERENCES CITED The following references are of record in the file of this patent:

FOREIGN PATENTS Number Country Date 85,588 Germany Feb. 13, 1896 510,447 Germany Oct. 18, 1930 OTHER REFERENCES Granger, Ind. Eng. Chem, vol. 24, No. 4, pp. 442-8 (April 1932) 7 pages. 

1. A PROCESS FOR PREPARING A COMPOUND OF THE GENERAL FORMULA, 